Certain phosphorus ester derivatives of 3-aminotriazole



United States Patent CERTAIN PBQSPHORUS ETER DERIVATKVES 8FS-AMINO'IRIAZOLE Jacques Meltzer, Kobus Weiliuga, and BernardusGerhardus van den Bus, all of Van Houteulaan, Weesp, Netherlands,assigncrs to North American Phiiips Company, Inc., New York, N.Y., acorporation of Delaware No Drawing. Filed Feb. 29, 1960, Ser. No. 11,452Claims priority, appiication Netherlands Mar. 3, 1959 '7 Claims. (Cl.2603t 8) This invention relates to new and novel phosphorus containingheterocyclic compounds, to methods of preparing these compounds and tothe use of said compounds as pesticides.

One of the most important needs in agriculaure is for pesticides whichare effective against crop destroying pests such as insects, mites, andfungi and which are at the same time relatively nontoxic to Warm bloodedanimals. The need for such pesticides is constantly increasing in viev.of the rapidly increasing demand for agricultural products.

It is a principal object then of this invention to produce new and novelphosphorus containing heterocyclic compounds.

It is another principal object of this invention to provide new chemicalcompounds which are useful for the destruction of plant harmful pestsand which are relatively harmless to warm blooded animals.

According to the invention new and novel phosphorus containingheterocyclic compounds are provided. These compounds correspond to thegeneral formula:

TrRr

T2R2 wherein Q represents an organic radical containing a heterocyclicring consisting of cmbon atoms and from 1 to 3 nitrogen atoms, two ofsaid nitrogen atoms being separated from each other by at least one ofthe ring carbon atoms, and joined to the phosphorus atom through a ringnitrogen, X represents a member of the group consisting of sulfur andoxygen, T represents a member of the group consisting of oxygen andsulfur, T represents a member of the group consisting of oxygen, sulfur,the radical NH and the radical NR wherein R represents an alkyl radicalcontaining from 1 to 5 carbon atoms and R and R each representsaliphatic hydrocarbon radicals. The heterocyclic nucleus may besubstituted or condensed with a substituted or unsubstituted benzenenucleus. However, the heterocyclic ring should have aromatic properties.

Examples of heterocyclic radicals that may be represented by Q are theradicals of pyrrole, pyrazole, irnidazole, 1,2,4-triazole, indole,carbazole, benzimidazole and substituted products thereof.

These heterocyclic radicals may be substituted with alkyl, alkenyl,cycloalkyl, cyclo kenyl, aryl, aralkyl, aralkenyl, alkylamino,dialkylamino, arylamino, diarylamino, acylamino, alkoxy, andalkylmercapto substituents containing from 1 to 18 carbon atoms, halogenatoms preferably chlorine atoms, the nitro, amino, ureido, carboxy,carbalkoxy and sulfone radicals. Best results are achieved when thereare five carbon atoms in the heterocyclic ring and the ring issubstituted with one or more alkyl radicals containing from 1 to 7carbon atoms, a phenyl group and in particular an amino group.

Compounds of the invention in which Q represents the radicals,3-amino-l,2,4-triazolyl; 3-amino-5-alkyl- 1,2,4-triazolyl in which thealkyl group contains from 1 to 7 carbon atoms and3-amino-5-phenyl-1,2,4-triazolyl and in which R; and R are alkyl groupscontaining 3 ,111,525 Patented Nov. 19, 1963 from 2-5 carbon atoms inparticular ethyl and isopropyl have been found to be the most effectivepesticides.

These compounds are very useful in combating plant harmful pests such asinsects and mites especially spider mites and also moulds. In addition anumber of these compounds are useful as plant growth regulators.

In particular, it has been found that the O,O-dielhyl phosphoryl and the0,0-diethyl-thionophosphoryl derivatives of 3-amino-1,2,4 triazole,5-phenyl-l,2,4-triazole and 3-amino-5-alkyl-1,2,4-triazole in which thealkyl group contains from 1 to 7 carbon atoms are effective pesticides.

The compounds of the invention may be prepared in such a manner that thephosphoryl thiophosphoryl group is introduced into the cyclic nitrogencontaining heterocyclic compound in one or two reaction stages.

Thus according to one method of the invention the heterocyclic compoundQH wherein H is the hydrogen atom attached to a ring nitrogen or thecompound QMe wherein Me is a metal atom preferably sodium or potassiumattached to a ring nitrogen and wherein Q has the indicated meaning isreacted with a compound corresponding to the general formula T2R2wherein Hal represents a halogen atom such as iodine :or fluorine butpreferabiy chlorine, X represents oxygen or sulfur, T represents oxygenor sulfur, T represents oxygen sulfur, the radical =NH or the radical=NR wherein R represents an alkyl radical containing from 1 to 5 carbonatoms, and n represents 0 or 1. This reaction is preferably carried outin the presence of a hydrogen halide binding agent particularly if thereactant QH is employed. If n has the value 0 in the product Tin,

TzRg this material is oxidized or sulfurized. In another method thecompound Hal HalP (X)n HaI wherein Hal, X and n have their previouslydesignated meanings is reacted with the compound QH or QMe and theresultant product which has the formula Hal Q (X)n Hal is then reactedwith an alcoholate or a thiolate preferably a sodium alcoholate or asodium thiolate. The heterocyclic compound produced may be oxidized orreacted with sulfur if n=0 depending upon whether X represents oxygen orsulfur in the final product.

In still another method of preparing the compounds of the invention, thecompound QH or Me is reacted with a compound corresponding to thegeneral formula:

to yield a compound corresponding to the general formula and thishalogen containing heterocyclic compound is then reacted with a memberof the group consisting of 3 alcoholates and thiolates to produce acompound corresponding to the general formula of3-amino-5-phenyltriazole-1,2,4 in 109 ml. of acetonitrile. Subsequentlythe resulting mixture Was stirred at 35-40 C. for two hours and thenconcentrated by TiRl evaporation in vacuo. The residue was extractedwith n 5 acetone, the acetonic solution concentrated by evapora- TzRztion and the residue, an oil, was Washed with petroleum Here too when nrepresents 0 the product is oxidized or ether (boiling range s Yield:60% sulfllf'izei The Examples II-XI and XVI, given in Table I, have TheIeactlons 1n Whlch hj compounds of the cychc been carried out in amanner analogous to that of Exnitrogen containing heterocyclic compoundare not used, ample L Included in Table I are also the Examples canadvantageously be carried out 111 the presence of a XHLW which have hemGarfield out in a manner hydrogen halide binding agent. As such theremay be nalogous to that of Example XII given below. In Exused amines andparticularly tertiary ammes, for example ample XV the Potassium compoundhas been used as trialkylamines, e.g. tr-imethyland tr1ethylarn1ne andstarting materiaL N,N-dialkylanflines and f f P h? and parhculafly inTable I are successively stated the numbers of the hOmOIPgUeS thereof,the Plcohhes, hlhhhnes and colhdme examples, the starting materials, thediluting agents, the and IIllXmIes of 51659 h h reaction temperature,the yields of resulting products, cal- Anothel" l? of acld'bmdmg agentswhlhh may he culated on the quantities of cyclic nitrogen containing f Py COIPPTISES mfg/{a1 conipfiunds h Sodlum, Poms heterocyclic compoundused, the physical constants of Slum, magfleslum, Calcium, h and Zinc:Such as the resulting products. Of the physical constants a boilides,hydroxides, carbonates, brcarbonates, alcoholates ingpoint or a meltingPoint is given The boiling point a CaTbQXYhC Saltsis indicated by F,followed by the temperature in C. These Processes of prepafmg compoundsof and the relative pressure in mm. of mercury. The meltinvention arepreferably carried out 1n the presence of a ing point expressed in o Cis indicated by solvent for the cyclic nitrogen contammgheterocychc theExamples 1, H, IV, V V111, XIV and m compound. According to the natureof this compound .0,() diethylphosphorylchloride is used, in theExamples and its substituents, a nonpolar or polar solvent is In, VI VHIX, XII, Xiv and XV, O,0 dithy1thiO chosen. As such solvents there maybe used for exphosphmylcmoride, and in me Examples X and XI amplealiphatic and aromatic hydrocarbons, forexamdidsopmpylphosphorylchloride ple hexane, petroleum ether and b nz et a In the Examples I-XI collidine was used as the hydrotertiary amines,for example pyridines, mtriles as acetogen acid binding agent. nitrile,ketones as acetone and methylethylketone, esters EXAMPLE XII as ethylacetate, alcohol, for example methanol and ethanol, and further forexample nitrobenzene, carbon tetra- P the sodlhm comPouhd of mdole,obtalmajd chloride and dimethylformamida lgy the action of sod1um onmdole were suspended m In cases wherein a metal compound of the cyclicnitroof h Whlle lrrmg the resulting susgen containing heterocycliccompound is used as a starti il h 0f g- Of 11ethy1th1onophosingmaterial, polar solvents, for example acetonitrile, are P Or/lc g 1h 20of acetomml? was added at preferreci about 1015 C. At the end of thereaction the separated In order that the invention may be readilycarried into 40 Sodlhm h d W filterhd P filtrate evaporated efifect itwill now be described in greater detail with refand h Tesldue dlssolvefi1h dlethyl f Thehthereal erence to the examples and tables which follow.Sohlhoh was Washed w Watch dnhd on Sodium F The values calculated forthe contents of warious ele- Phate g afthjr h cohcehhhated h evaporationments in the resulting products givan in the examples, The resulting oilwas distilled. Boilingpomt 112-114 C. relate to a compound formed from 1mol of the cyclic at 0-005 mercury @resshrh Yleldnitrogen containingheterocyclic compound and 1 mol h the Examples Y T an h of thephosphorus containing non-heterocyclic reactant. almdhphosphorylchloride 13 used the Phosphonfemus Table I summarizes the data of theexamples. mac/[10h h h The Examples XVHLXYI have Table II gives thenames of the final products obtained been harmed out 111 manneraha'logc'us to that of in the examples. 5O ample XVII- EXAMPLE I EXAMPLEXVII 6.05 g. of collidine and 8.8 g. of diethylphosphoryl- A mixture of8.4 g. of 3-aminotriazole-l,2,4, 12.1 g. chloride were successivelyadded to a suspension of 8 g. of collidine, 70 cc. of acetonitnle and17.2 g. of O-ethyl- Table I Number Starting material Diluting AgentReact. temp. gg Physical con- Example in 0. percent stants3-amino-5-phenyltrimole-1.2.4". acetonitril 35-40 60 (011.)3-amiuotriazole-1.2.4 aceton 20 to 30 a 68 (011.) do 10 s=s2-s503-amino-5-pentyltriazole-12.4. 40 (oil; 3-amino-5-methyltriazole 2.4(oil. 3-amino-5-pentyltriazole-1.2.4- 100 (oiL)3-amino-5-methyltriazole-1.2.4-. -do (oiL) 3-amin05-ethyltriaz0le-1.2.42100111525..-. 84 (oil) do do about 15 73 (oil)3-amino-5-pentyltriazole-L2.4 diethyl ethen. about 35 S=5354 C3-aminotriazole-l.2.4 acetonitrile about 45 100 (oil) Indol o about 15--es F=112-1l40 at 0.005 mm lo d0- do--- 51 F=110112 o 0.01 mm.3-amino-5-phenyltriazole-1.2.4 lo- -80 51 5:63-65 0 carhzmlo (10 60-7063 2-arninobenzirnidazole acetone about 50 30 S=228229 C3-amin0triazole-1.2.4 acetonitrrle about; 20 82 S=576& C3-amino-5-pentyltriazole-12.4 diethylether 35 76 3-amiuotriazole-l.2.4acetom'trile 60-70 64 S=108l10O 3-amino-5-pentyltriazole-l.2.4 benzene66 (oil.)

5-phenyl 3-aminotriazole-l2.4 acetonitrile 8:104-105" 0.

5 N-dimethylamidophosphorylchloride was stirred at about 20 C. for 90minutes. Then the solvent was distilled oil and the resulting residuewas extracted with Ibenzene. The benzene solution was concentrated byevaporation and the obtained residue was washed with petroleumether(boiling range 4060 C.). Yield: 18 g. (Y.:

82%). Mel-ting point: 5764 C.

Table 11 Example No. Product N-( 0. O-diethylphosphoryl)-3-amino-5-phenyltriazole-N-(0.0-diethylphosphoryl)-3-aminotriazole-l.2.4. N-(O.O-diethylthionophosphoryl)-3-aminotriazole-1.2.4.N-(O.O-diethylphosphoryl)-3-amino-5-pentylt1-iaz0le- .4. N-( O. O-diethylphosphoryl)-3-amino-5-met hyltriazole- N-(O.O-dlethylthionophosphoryl) 3-amin0-5- pentyltriazole-LZA.

N-(0.0-diethylthionophosphoryl)-3-amino-5-methyltriazde-LZA.

N- O O-diethylphosphoryl) -3-amino-5-et hyltriazole- N-(O. O-diethylthionophosphoryl)-3-amino-5-ethy1- triazole-L2A.N-(0.0-di-isopropylphosphory1)-3-amino-5-pentyltriazle-L2A. N-(0.0di-isopropylphosphoryl) 3-aminotriazole- XX N-(O-isopropylN-dimethylamidophosphoryl)-3- amino-5-pentyltriaZole-1.2.4. XXIN-(O-isopropy1N-dimethylamidophosphoryl)-3- amino-fi-phenyltriazolel2.4.

The active compounds of the invention may be formulated and employed inthe conventional manner for destroying the noxious organisms. Thus theymay be mixed with solid carriers, ground to the desired particle sizeand dusted on the crops. xamples of the solid carriers that may beemployed are pipe clay, diatomaceous earth, kaolin, dolomite, talcum,gypsum, bentonite, attap-ulgite, kieselghur, celite, wood meal, tobaccodust, ground walnut shells and ground cocoanut shells. In these duststhe concentration of the active compound usually lies between :aboutl22% by weight.

The active compounds of the invention may also be applied to the cropsin the form of suspensions in a volatile liquid usually water. Inpreparing such a suspension the active compound is formed into awettable powder and then dispersed in a volatile solvent such as water.In the formulation of the wettable powder the active compound is groundwith a solid carrier of the type employed in forming a dust and asuitable dispersion agent such as a lignin sulfonate or a naphthalenesulfonate and/or a suitable wetting agent such as a fatty acidsulfonate, an alkaryl sulfonate or an acid condensation product of thetype sold under the trademark Igepon are added. In the wettable powderthe concentration of the active compound may vary between wide limits.However, a concentration of between about to 80% by weight is usuallypreferred.

Finally the active compounds of the invention may be applied to thecrops in the form of emulsions in water or other volatile liquids. Inpreparing these emulsions the active compound is first formed into amiscible oil. These miscible oils contain besides the active compound aWater insoluble solvent for the active compound and an emulsifier. Amongsolvents that may be employed are Xylene, toluene, dioxane, aromaticpetroleum distillates such as solvent naphtha, distilled tar oil,tetralene and cyclohexane and mixtures of these liquids. Among theemulsifiers that may be employed are the 'alkyl phenoXyglycol ethers,polyoxyethylene. sorbitan esters of fatty acids,polyoxyethylene-sorbitol esters of fatty acids and the emulsifiers knownby the trademarks Tween, Triton and Atlox. The concentration of theactivecompound in the solvent is usually about 250% by weight and in theemulsion the concentration of the active compound is usually betweenabout 0.01 to 0.5% by weight.

While we have described our invention in connection with specificembodiments and applications, other modifications thereof will bereadily apparent to those skilled in this art without departing from thespirit and scope of the invention as defined in the appended claims.

What is claimed is:

1. A triazolyl phosphorus compound of the formula wherein Q is3-amino-l, 2,4-triazolyl substituted in the 5 position only with up toone alkyl of 1 to 7 carbon atoms, the phosphorus is directly attached toa ring nitrogen and R and R are each alkyl of 2-5 carbon atoms.

2. A triazolyl phosphorus compound of the formula wherein Q is3-amino-1,2,4-triazolyl substituted in the 5 position only with up toone alkyl of 1 to 7 carbon atoms, the phosphorus is directly attached toa ring nitrogen and R and R are each alkyl :of 2-5 carbon atoms.

3. A 3 amino-5-phenyl-1,2,4-triazolyl phosphorus compound of theformula.

wherein Q is 3-arnino-5-phenyl-1,2,4-triazolyl, R and R are each 'alkylof 2 to 5 carbon atoms and the phosphorus is directly attached to a ringnitrogen.

4. A 3aamino-5-phenyl-l,2,4-triazolyl phosphorus compound of theformula.

References Cited in the file of this patent UNITED STATES PATENTS Joneset al June 7, 1955 Coover et al June 19, 1956 (Other references onfollowing page) UNITED STATES PATENTS OTHER REFERENCES 2,844,582 R a1eyJuly 22, 1958 Frear et 21.: I. of Economic Entomology, v01. 40, pp2,888,379 Brunin-g May 26, 1959 736-741 (1947). 2,953,491 Hardy et a1Sept, 20, 1960 5 A son et a1-: Chem. Abstracts, Vol. 52, cal. 11538(1958). FOREIGN PATENTS Chemical Abstracts, index 10 vol. 53, p. 2114s1959 713,278 Great Britain Aug. 11, 1954 Coe et 211.: Chem. Abstracts,Vol. 53, col. 19285 (1959).

1. A TRIZOLYL PHOSPHORUS COMPOUND OF THE FORMULA